The surprising answer to the question Are the structural characteristics of the product of the nucleophilic addition to complex 1 those of a cyclohexadienyl complex (2 a) or those of a diene aza-enolate complex (2 b)? is: both. This is indicated by the X-ray structure determination of the complex with R=naphthyl. An unprecedented endo-hydride abstraction concludes the sequence that provides a new route to 1,2-substituted planar chiral [(n6-arene)Cr(CO)3] compounds.